PL124785B1 - Fungicide and method of manufacture of substituted n-propargylanilines - Google Patents

Fungicide and method of manufacture of substituted n-propargylanilines Download PDF

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Publication number
PL124785B1
PL124785B1 PL1979219330A PL21933079A PL124785B1 PL 124785 B1 PL124785 B1 PL 124785B1 PL 1979219330 A PL1979219330 A PL 1979219330A PL 21933079 A PL21933079 A PL 21933079A PL 124785 B1 PL124785 B1 PL 124785B1
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formula
radical
wz0r
alkyl radical
hydrogen atom
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PL1979219330A
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PL219330A1 (en
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Bayer Ag
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Priority claimed from DE19782847287 external-priority patent/DE2847287A1/en
Priority claimed from DE19792927461 external-priority patent/DE2927461A1/en
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Publication of PL219330A1 publication Critical patent/PL219330A1/xx
Publication of PL124785B1 publication Critical patent/PL124785B1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/88—Carboxylic acid amides having nitrogen atoms of carboxamide groups bound to an acyclic carbon atom and to a carbon atom of a six-membered aromatic ring wherein at least one ortho-hydrogen atom has been replaced
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Furan Compounds (AREA)
  • Pyrane Compounds (AREA)

Description

Przedmiotem wynalazku jest srodek grzybobójczy oraz sposób wytwarzania nowych podstawionych N-propargilo-anilin stanowiacych substancje czyn¬ na srodka.Wiadomo, ze chlorowcoacetanilidy, na przyklad ester alkilowy N-chloroacetylo-N-(2,6-dwumetylo- fenylo)-alaniny lub -glicyny, mozna z powodzeniem stosowac do zwalczania grzybic roslinnych (opis RFN DOS 2 350 944 i opis patentowy St. Zjedn. Am. nr 3 780 090). Dzialanie ich jednak, zwlaszcza w niz¬ szych dawkach i stezeniach, szczególnie przy zwal¬ czaniu rodzajów Phytophthora, nie zawsze jest w pelni zadowalajace.Stwierdzono, ze silne wlasciwosci grzybobójcze wykazuja nowe podstawione N-propargilo-aniliny o ogólnym wzorze 1, w którym R1 oznacza atom wodoru, rodnik alkilowy lub chlorowiec, Rf ozna¬ cza atom wodoru lub rodnik alkilowy, R* oznacza atom wodoru lub rodnik alkilowy, RA oznacza atom wodoru lub rodnik alkilowy, R6 oznacza atom wodoru, rodnik alkilowy, chlorowiec lub ewentual¬ nie podstawiony rodnik fenylowy, R« oznacza rod¬ nik czterowodorofurylowy, tiofenylowy, czterowodo- rotiofenylowy, ewentualnie podstawiona rodnikami alkilowymi grupe izoksazolilowa, ewentualnie pod¬ stawiony grupa cyjanowa lub tiocyjanowa rodnik alkilowy, alkenylowy i alkinylowy, grupe dwuchlo- rowcoalkilowa, jak równiez grupy -CHj-Az, -CH2- -OR8, -CHfSR*, -OR7, -SR7, -CH2-OS02R8 -COOR7 i grupe o wzorze 4, przy czym R7 i R1 oznaczaja pod¬ stawiony chlorowcem, grupa cyjanowa i tiaeyjano- wa rodnik alkilowy i ewentualnie podstawiony rod¬ nikami alkilowymi rodnik alkenylowy, alkinylowy lub alkoksyalkilowy, R7 oznacza ponadto niepodsta- 5 wiony rodnik alkilowy, a Az oznacza grupe pirazo- lilowa-1, 1,2,4-triazolilowa-1 i imidazolilowa-1.Sposobem wedlug wynalazku nowe podstawione N-propargilo-aniliny o wzorze 1 otrzymuje sie w ten sposób, ze N-propargilo-analiny o wzorze \ w któ- 10 rym R1 — R5 maja znaczenie wyzej podane, podda¬ je sie reakcji z chlorkami lub bromkami wzglednie bezwodnikami kwasowymi o wzorach 3a lub 3b, w których R6 ma znaczenie wyzej podane, w obec¬ nosci rozcienczalnika i ewentualnie w obecnosci 15 srodka wiazacego kwas.Nowe podstawione N-propargilo-aniliny wykazu¬ ja silne wlasciwosci grzybobójcze, przy czym nie¬ oczekiwanie nowe sbustancje czynne sa znacznie ak¬ tywniejsze niz znane estry alkilowe N-chloroacety- 20 lo-N-(2,6^dwumetylofenylo)-alaniny lub -glicyny.Nowe podstawione N-propargilo-aniliny sa ogól¬ nie okreslone wzorem 1. We wzorze tym R1, R», R* R4 i R5 oznaczaja korzystnie wodór i prosty lub rozgaleziony rodnik alkilowy o 1—4 atomach wegla, 25 R1 oznacza poza tym korzystnie chlorowiec, zwlasz¬ cza fluor, chlor lub brom, R5 oznacza ponadto ko¬ rzystnie rodnik fenylowy ewentualnie podstawiony chlorowcem,, rodnikiem alkilowym o 1—4 atomach * wegla i grupa nitrowa, oraz oznacza atom chlorow- 30 ca, R6 oznacza korzystnie grupe czterowodorofury- 124 789u ooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo-noo coeoe«c*<»c«wcoc«c«eoc«coeocococoeoeo 05 05 Oi OS OJ 05 OJ 05 05 OJ Oi O* 05 OJ OS O) 05 05 OJ 05 O Cb 05 05 Oi O) 05 Oi OJ 05 Oi O) 05 O Oi Oi 05 05 05 OS Oi 05 OS Oi Oi OJ 05 05 05 Oi 05 05 Oi 05 Oi Oi 05 05 Oi Ci _. /-s 1 1 1 1 1 1 1 1 1 1 1 1 1 1 II 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I I 1 1 1 1 I 1 1 1 I l l 1 l 1 1 I I 1 I 1 I 1 1 1 I I 1 ££ lcowcoeoc*coeoc*»c«eoe«cocoeocococ«cococ*eocococococococococoeococococo ffipHSffiKwHHffiHWWWWHWHHwffiffiffi 1 co co coceeocoeocococococoeococococo 0 1 cococococococoeocoeocoeocococo Ml 1 1 1 1 M * * * 1 M 3 3| 1 1 1 1 ¦ M 3 * * 1 M 3 *il | | | | M^^^GM-^^I 1 1 1 1 M 3 * * 1 \ z z z \ g, o o o o o o g, g, g, g o o g, g, g, o o o o o o g, g, g, g, o o g, g, g, o o o o o o g, g, g. g, B o g, g, g, o o o o o o g, g. g, g, o o g. g, g, o owG",PG ó <" owSBP0 oo ooog-oo° Ko o w C m o g ^p o bo* &p f:ffi pgp yx f:K po? &p p pop j,p f^ a 1 M £P co .rr1 » eo ?""< eo l"1 *S M Ol t9 o o o O O O V 1 1 U to co ^ en 05 1 5 Pd Pd Ol roooooooooooonoooooooooooooooooooooooooooooooooooooooooooooooooooo oatoMOaMtteoMeaeoeoMeooattMetoseoMeoMoaMeoeaeaeoaaoaiMco&aMaaGOMeoMCottoateeootM O)O)O)O)O)O)O)O)0)O)O)O)O)O)O)O)O)O)O) 0)0)0)0)0)0)0)0)0)0)0)0)0)030)0)010)0)0)0)0)00)0)0)00)0) *Oi — — — — _„ —— _. _» _„ _. _„ _. _. 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I I I I I I I I I II I I ML opooooooooooopooooooooo<"ooooooooooooooooooooooooooooooooooooooooo XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX X X X X Q X WKWWEWfflffiEWKfflEWWKEEti^KWE.ffiEEfflEEEffl 09 W G» ffiffiffiooooooooooooo to 00 Ul S I S • « b o a- t» o im i <.G & ft ffi ffi ffi -» -» fu hj O to o X 8 o o Ml HM o g. o o o o g. a ^ o a w w i W -O O-o ¦£,« O Q " w o O w 3 1 1 1 1 1 g,o o o o o « X X O X X en to to /-*\ to (o O ° n S O w Q co" Q *°ff^ tr X * * z N O _ _ »-l »-s »-i «-i H (O 00 ^ n KM t» to O O 1111113 3 3 3 o o o o o o g, g, g, g.O O X U O w X M CO 00 ^ 3 3 3 6 ó g, * fc? to _ O O ^ X * to I 8 to I I I I I I O O O O O O K X O X X X o o g Q co % 5 owGM po 3 3 N N M CO 00 ^' o X 1 o I o X l I 3 5: o&g- b ^ • O124 785 7 8 1 1 CH8 CH3 CH8 CH3 CH8 CH8 CH3 CH8 CH8 CH3 CH8 CH3 CH8 •CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 ^H8 CH8 CH8 CH8 CH8 CHg CH8 CH3 CH3 CH3 CH8 , CH3 CH8 CH8 CH8 | CH8 CH8 CH8 CH8 CH8 CH8 CH8 C2H5 1 CeH5 C2H5 c^ CsHg C*H5 CaU C2H5 C*H5 C*H5 C2H5 C8H5 C2H5 C2H5 C*H5 " C*H5 C2H5 | C2H5 1 1 2 l 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 I 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C*H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 I 6—C2H5 6—C2H5 6—C2H5 | 6-CH, 6—C2H5 6—C2H5 6—CfHs 6—C2H5 C—C2H5 1 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H11 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 | 3 T H H H H H H H H H H H H H * H H H 1 H H H H H H H H H H H H H H H H H H* H H H H H H H H H H H 1 H H H H H H H H H H H H H H H H H H H H 1 4 H H H 1 H H H H 1 H H H H H H H H H H CH3 CH8 CH3 CH3 CH3 CH3 CH8 CH8 CH3 .CHg H , H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH3 | 1 5 1 CH3 CH3 CH8 CH3 CH8 CH3 CH3 Br Br Br Br » Br Br Br Br Br Br Br Br Br Br Br Br Br Br Br Br Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl J J J J J J J J J J H H H H H H H H H H H H H H H H H H | 1 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCH3 wzór 8 —CH2SCH3 wzór 4 —CH2OCH3 wzór 5 wzór 6 —CH2OC2H5 1 —CH2OS02CH3 1 —CHCI2 ' —COOCHg wzór 8 —CH2SCHg wzór 4 —CH2OCH3 wzór 5 wzór 6 —CH2OC2H5 —CH2OS02CH3 —CHCI2 —COOCH3 wzór 8 —CH2SCH2J wzór 4 CH2OCH3 | wzór 5 wzór 6 —CH2OC2H5 —CH2OS02CH3 —CHCI2 —COOCH3 wzór 8 —CH2SCH3 wzór 4 —CH2OCH3 wzór 5 wzór 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCH3 wzór 8 —CH2SCH3 J wzór 4 1 —CH2OCH3 wzór 5 wzór 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCHg 1 wzór 8 —CH2SCH3 wzór 4 —CH2—OCH3 wzór 5 wzór 6 —CH20C2H5 —CH2OS02CH3 —CHC12 —COOCH8 wzór 8 '124 785 10 1 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C,H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 CZH5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 2 . 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—*C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—-C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6^C2Hs 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6-C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 6—C2H5 3 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H 4 CH3 CH8 H H H H H H H H H H H H H.H H H H H H H CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 H H H H H H H H H H H H H H H H H H H H 5 H H CH3 CH3 CH3 CH3 CH8 CH3 CH3 CH3 CH3 CH3 Br Br Br Br Br Br Br • Br Br Br Br Br Br Br Br Br Br Br Br Br Cl Cl x Cl Cl Cl Cl Cl Cl Cl Cl J J J J J J J J J J 6 —CH2SCH3 wzór 4 —CH2OCH3 wzór 5 wzór 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCH3 wzór 8 —CH2SCH3 wzór 4 —CH2OCH8 wzór 5 wzór 6 —CH2OC2H5 —CHzOSOaCH* —CHC12 —COOCHg wzór 8 —CH2SCH3 wzór 4 —CH2OCH8 1 wzór 5 wzór 6 —CH2OC2H5 —CHaPSOaCHs —CHC12 —COOCHg wzór 8 —CH2SCH3 wzór 4 —CH2OCH3 wzór 5 wizór 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCH3 wzór 8 —CH2SCH3 wzór 4 —CH2OCHa wzór 5 wzór 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCHg wzór 8 —CH2SCH3 wzór 4 Iowa, tiofenylowa, czterowodorotiofenylowa, ewen¬ tualnie podstawiona rodnikiem metylowym lub ety¬ lowym grupe izoksazolilowa oraz ewentualnie pod¬ stawiony grupa cyjanowa lub tiocyjanowa rodnik alkilowy o 1—4 atomach wegla i rodnik alkenylowy oraz alkinylowy kazdorazowo o 2—4 atomach we¬ gla, ponadto korzystnie oznacza grupe dwuchlo- rowcoalkilowa o 1—2 atomach wegla, przy czym jako atomy chlorowca wymienia sie korzystnie fluor i chlor, jak równiez oznacza grupy -CH2-Az, -CHr 66 -OR8„ -CH2-SR7, -OR7, -SR7, -CH2-OSO2R8, -COOR7 i grupe o wzorze 7, Az oznacza korzystnie grupe pirazolilowa-1, 1,2,4-triazolilowa-l i imidazolilo- wa-1, R7 oznacza korzystnie ewentualnie podstawio¬ ny chlorowcem, zwlaszcza fluorem, chlorem i bro¬ mem, grupe cyjanowa i tiocyjanowa rodnik alkilo¬ wy o 1—4 atomach wegla oraz grupe alkoksyalkilo- wa o 1—4 atomach wegla w kazdym rodniku alki¬ lowym.Szczególnie korzystne sa podstawione N-propar-124785 11 12 gilo-aniliny o-wzorze 1, w którym R1, R2 i R3 ozna¬ czaja atomy wodoru, rodniki metylowe, etylowe, izo¬ propylowe, II-rzed. butylowe i IH-rzed. butylowe, Ri oznacza ponadto chlor lub brom, R4 oznacza atom wodoru, rodnik metylowy lub etylowy, R5 oznacza atom wodoru, rodnik metylowy, etylowy, fenylowy, brom, chlor lub jod, a R6 oznacza grupe 2-tienylo- wa, 2-czterowodorofurylowa, 5-metyloizoksazolilo- wa-3, metoksymetylowa, etoksymetylowa, alliloksy- metylowa, propargiLoksymetylowa, etoksymetoksy- metylowa, metylotiometylowa, metoksylowa, etoksy- lowa, metylotio, metylosulfonyloksymetylowa, meto- ksykarbonylowa, etoksykarbonylowa, dwuchlorome- tylowa, pirazolilo-1-metylowa, imidazolilo-1-metyIo¬ wa, 1,2,4-triazolilo-l-metylowa i czterowodoropiran- -2-yloksy-metylowa.Jako szczególnie korzystne wymienia sie zwiazki o wzorze 1 zebrane w tabeli 1.W przypadku stosowania na przyklad 2,6-dwume- tylo-N-propargilo-aniliny i chlorku kwasu furano- -2-karboksylowego jako zwiazków wyjsciowych, przebieg reakcji przedstawia podany na» rysunku schemat.Stosowane jako zwiazki wyjsciowe N-propargilo- aniliny sa ogólnie okreslone wzorem 2. We wzorze tym R1, R2, R*, R4 i R5 oznaczaja korzystnie grupy wymienione juz jako korzystne przy omawianiu zwiazków o wzorze 1.N-propargilo-aniliny o wzorze 2 sa po czesci zna¬ ne (opisy patentowe St.Zjedn.Am. nr 3 535 377 i 4 001 325), wzglednie mozna je wytwarzac w znany sposób, np. przez reakcje odpowiednich anilin z ha¬ logenkami o wzorze 5 albo odpowiednimi sulfonia¬ nami propargilu, na przyklad z mezylanami lub to- zylanami, w obecnosci srodków wiazacych kwas, np. weglanu sodu lub potasu, ewentualnie w obec¬ nosci obojetnego rozpuszczalnika organicznego, ta¬ kich jak etanol, w temperaturze 20—150?C, przy czym* korzystnie mozna stosowac nadmiar aniliny.N^propargilo-aniliny o wzorze 2, w którym R4 oznacza rodnik metylowy, mozna otrzymac tez przez reakcje odpowiedniej aniliny z acetylenem w obec¬ nosci acetylenfcu miedzi pod cisnieniem (Liebigs Ann.Chem. 596, 1 (1955)).Jako przyklady zwiazków o wzorze 2 wymienia sie zwiazki zebrane w tabeli 2.Stosowane ponadto jako zwiazki wyjsciowe chlor¬ ki lub bromki wzglednie bezwodniki kwasowe sa ogólnie okreslone wzorami 3a i 3b. We wzorach tych R6 korzystnie oznacza grupy wymienione juz jako korzystne przy omawianiu zwiazków o wzorze 1.Chlorki lub bromki wzglednie bezwodniki kwaso¬ we o wzorach 3a i 3b sa zwiazkami ogólnie znany¬ mi w chemii organicznej.Jako rozcienczalniki stosuje sie korzystnie oboje¬ tne rozpuszczalniki organiczne. Naleza do nich 'ko¬ rzystnie ketony, takie jak dwuetyloketon, zwlaszcza aceton i metyloetyloketon, nitryle, takie jak propio- nitryl, zwlaszcza acetonitryl, etery, takie jaik cztero- wodorofuraiL lub dioksan, weglowodory alifatyczne i aromatyczne, takie jak eter naftowy, benzen, to¬ luen lub ksylen, chlorowcowane weglowodory, takie jak chlorek metylenu, czterochlorek wegla, chloro¬ form lub chlorobenzen oraz estry, jak octan etylu..Reakcje mozna ewentualnie prowadzic w obec- Tabela 2 i R1 CHg C2H5 C2H5 C(CH3)3 CHa CU, Cl Cl CH* CH3 C2H5 C2H5 CH3 C2H5 C2H5 CH* C2H5 C2H5 CHa C2H5 1 C2H5 1 CHo C2H5 C2H5 | R2 6—CH3 6—C2H5 6—CH3 H 3—CH3 5—CHa 1 6—CH3 6—C(CH3)3 3—CH3 6—CH3 6—C2H5 6—CH3 6—CH3 6—C2H5 6—CH3 6—CH3 6—C2H5 6—CH3 6-CHg , 6—C2H5 6—CH3 6-CH3 6—C2H5 6—CH3 R» H H H H H H H B 6-<:h3 H H H H H H H H H H H H H H H | | R4 H H H H H H H H H CHs CHs CHs C2H5 C2H5 C2Es H H H H H H CHa CH3 CH3 1 R5 H I.H H H H :h H H H H H H H H ' H CH3 CH3 CH3 wzór 11 wzór 11 wzór 11 CH3 CH3 CH3 nosci srodków wiazacych kwas (akceptory chlorow¬ cowodoru). Mozna tu stosowac wszelkie znane srod¬ ki wiazace kwas. Naleza do nich korzystnie zasady organiczne, takie jak aminy trzeciorzedowe, na przy¬ klad trójetyloamina, albo pirydyna, ponadto zasady nieorganiczne, takie jak wodorotlenki metali alka* licznych i weglany metali alkalicznych. Mozna rów¬ niez stosowac katalizator, taki, jak dwumetylofor- mamid.Temperatura reakcji-;moze sie zmieniac w szero¬ kim zakresie. Na ogól reakcje prowadzi sie w tem¬ peraturze 0—120°C, korzystnie 20—100°C, Do reakcji reagenty wprowadza sie korzystnie w ilosciach molowych. Zwiazki o wzorze* 1 wyod¬ rebnia sie w znany sposób.Produkty koncowe wyodrebnia sie w znany spo¬ sób.Nowe substancje czynne wykazuja silne wlasci¬ wosci mikrobobójcze i mozna je stosowac w prak¬ tyce do zwalczania niepozadanych mikroorganiz¬ mów. Substancje te nadaja sie do stosowania jako srodki ochrony roslin.Srodki grzybobójcze w dziedzinie ochrony roslin stosuje sie do zwalczania Plasmodiophoaromycetes, Oomycetes, Chytridiomycetes, Zygpmycetes, Asco- mycetes, Basidiomycetes, Deuteromycetesv Ze wzgledu na to, ze rosliny wykazuja dobra to¬ lerancje w stosunku do nowych substancji czynnych w stezeniach niezbednych do zwalczania chorób roslin, substancje te mozna stosowac do traktowa¬ nia nadziemnych czesci roslin, sadzonek i materialu siewnego oraz gleby.Nowe substancje czynne jako srodki ochrony ros¬ lin mozna stosowac z dobrymi wynikami do zwal¬ czania Oomycetes, np. przeciwko patogenom zarazy ziemniaczanej na pomidorach i ziemniakach (Phy- tophthora infestans). Nalezy szczególnie podkreslic, 10 15 20 25 30 35 40 45 50 55 6013 124786 14 ze nowe substancje czynne wykazuja nie tylko dzia¬ lanie zapobiegawcze, ale równiez dzialanie leczniczo/ /wypleniajace. Ponadto maja wlasciwosci systemicz- ne. Takie wiec rosliny mozna chronic przed zaka¬ zeniem grzybem, jezeli sbustancje czynna doprowa¬ dza sie poprzez glebe i korzenie albo poprzez nasio¬ na do nadziemnych czesci roslin.Substancje czynne mozna przeprowadzac w znane preparaty, takie jak roztwory, emulsje, proszki zwil- zalne, zawiesiny, proszki, srodki do opylania, pian¬ ki, pasty, proszki rozpuszczalne,, granulaty, aerozole, koncentraty zawiesinowo-emulsyjne, pudry do ma¬ terialu siewnego, substancje naturalne i syntetycz¬ ne impregnowane substancja czynna, drobne kap¬ sulki w substancjach polimerycznych i w otoczkach do nasion, ponadto preparaty z palna wkladka, ta¬ kie jak naboje, ladunki, i spirale dymne i inne oraz preparaty ULV do mglawicowego rozpylania na zim¬ no i cieplo.Preparaty te mozna wytwarzac w znany sposób, na przyklad przez zmieszanie substancji czynnej z rozcienczalnikami, a wiec cieklymi rozpuszczal¬ nikami, znajdujacymi sie pod cisnieniem skroplony¬ mi gazami i/lub stalymi nosnikami, ewentualnie zzastosowaniem srodków powierzchniowo czynnych, na przyklad emulgatorów i/hib dyspergatorów i/lub srodków pianotwórczych. W przypadku stosowania wody jako rozcienczalnika mozna stosowac na przy¬ klad rozpuszczalniki organiczne jako srodki ulatwia¬ jace rozpuszczanie.Jako ciekle rozpuszczalniki stosuje sie na ogól zwiazki aromatyczne, takie jak ksylen, toluen albo alkilonaftaleny, chlorowane zwiazki aromatyczne lub chlorowane weglowodory alifatyczne, takie jak chlo- robenzeny, chloroetyleny lub chlorek metylenu, we¬ glowodory alifatyczne, takie jak cykloheksan lub parafiny, na przyklad frakcje ropy naftowej, alko¬ hole, takie jak butanol lub glikol oraz ich etery i estry, ketony, takie jak aceton, metyloetyloketon, metyloizobutyloiketon lub cykloheksanon, rozpusz¬ czalniki silnie polarne, takie jak dwumetyloforma- mid i sulfotlenek dwumetylowy, oraz woda.Jako skroplone gazowe rozcienczalniki i nosniki stosuje sie ciecze, które sa gazami w normalnej tem¬ peraturze i pod normalnym cisnieniem, takie jak gazy aerozolotwórcze, takie jak chlorowcoweglowo- . dory, a takze butan, propan, azot i dwutlenek we¬ gla.Jako stale nosniki stosuje sie naturalne maczki skalne, takie jak kaoliny, glinki, talk, kreda, kwarc, atapulgit, montmorylonit lub ziemia okrzemkowa i syntetyczne maczki mineralne, takie jak kwas krzemowy o wysokim stopniu rozdrobnienia, tlenek glinu i krzemiany: Jako stale nosniki dla granula¬ tów stosuje sie skruszone i frakcjonowane maczki naturalne, takie jak kalcyt, marmur, pumeks, sepio- lit, dolomit oraz syntetyczne granulaty z maczek nieorganicznych i organicznych, jak równiez granu¬ laty z materialu organicznego, takiego jak trociny, lupiny orzechów kokosowych, kolby kukurydzy i lo- i dygi tytoniu.Jako emulgatory i/lub srodki pianotwórcze sto¬ suje sie emulgatory niejonotwórcze i anionowe, ta¬ kie jak estry polioksyetylenu i kwasów tluszczo¬ wych, etery polioksyetylenu i alkoholi tluszczowych, < na przyklad etery alkiloarylopoligjikolowe, alkilosul- foniany, siarczany alkilowe, arylosulfoniany oraz hydrolizaty bialka. Jako dyspergatory stosuje sie na przyklad ligninowe lugi posulfitowe i metylocelu- 5 loze.Preparaty moga zawierac srodki zwiekszajace przyczepnosc, takie jak karboksymetyloceluloza, po¬ limery naturalne i syntetyczne, sproszkowane, ziar¬ niste lub w postaci lateksu, takie jak guma arabska, 10 alkohol poliwinylowy i polioctan winylu.• Mozna równiez dodawac barwniki, takie jak pig¬ menty .nieorganiczne, na przyklad tlenek zelaza, tle¬ nek tytanu, blekit zelazowy i barwniki organiczne, takie jak barwniki alizarynowe, azowe i metalofta- 15 locyjaninowe, a takze substancje sladowe, takie jak sole zelaza, manganu, boru, miedzi, kobaltu, molib¬ denu i cynku.Preparaty zawieraja na ogól 0,1—95% wagowych substancji czynnej, korzystnie 0,5—90% wagowych, 20 Nowe substancje czynne moga wystepowac w pre¬ paratach lub róznych postaciach uzytkowych w mie¬ szaninie z innymi znanymi substancjami czynnymi, takimi jak substancje grzybobójcze, bakteriobójcze, owadobójcze, roztoczobójcze, nicieniobójcze, chwas- 25 tobójcze, substancje chroniace przed zerowaniem ptaków, substancje wzrostowe, substancje odzywcze dla roslin i srodki polepszajace strukture gleby.Substancje czynne mozna stosowac same, w po¬ staci koncentratów lub sporzadzanych z nich przez 30 dalsze rozcienczanie postaci uzytkowych, takich jak gotowe do uzytku roztwory, emulsje, zawiesiny, proszki, pasty i granulaty. Srodki stosuje sie w zna¬ ny sposób, np. przez podlewanie, zanurzanie, oprys¬ kiwanie, rozpylanie, rozpylanie mglawicowe, paro- 35 wanie, wstrzykiwanie, szlamowanie, powlekanie, opylanie, rozsypywanie, zaprawianie na sucho, za¬ prawianie na wilgotno, zaprawianie na mokro, za¬ prawianie w zawiesinie lub inkrustowanie.Przy traktowaniu czesci roslin stezenie substancji 40 czynnej w postaciach uzytkowych moze zmieniac sie w szerokim zakresie. Na ogól stezenia te wyno¬ sza 1—0,0001% wagowych, korzystnie 0,5—0„OtJlr/o.Do traktowania materialu siewnego stosuje sie na ogól substancje czynna w ilosci 0,001—50 g na kg 45 nasion, korzystnie 0,01—10 g.Do traktowania gleby stosuje sie substancje czyn¬ na w stezeniu 0,00001—0,1% wagowych, korzystnie 0,0001—0,02%.Nastepujace przyklady blizej wyjasniaja wynala- 50 zek.Przyklad. I. Testowanie Phytophthora (pomi¬ dory) — dzialanie zapobiegawcze.Rozpuszczalnik: 4,7 czesci wagowych acetonu.Emulgator: 0,3 czesci wagowych eteru alkiloarylo- 55 poliglikolowego.W celu uzyskania korzystnego preparatu substan¬ cji czynnej miesza sie 1 czesc wagowa substancji czynnej z podana iloscia rozpuszczalnika i emulgato¬ ra i koncentrat rozciencza sie woda do zadanego o stezenia. Ciecza do opryskiwania spryskuje sie; do orosienia mlode rosliny pomidorów. Po osuszeniu oprysku rosliny pomidorów zakaza sie wodna za¬ wiesina zarodników Phytophthora infestans i utrzy¬ muje w komorze wilgotnej o 100% wzgednej wilgot- •5 nosci powietrza i temperaturze okolo 20°C, Po uply-15 124 785 16 wie 3 dni okresla Sie stopien zaatakowania roslin pomidorów. Uzyskane wartosci szacunkowe przeli¬ cza sie na wielkosci procentowe, przy czym 0% oznacza brak zaatakowania, a 100% oznacza, ze ros¬ liny zostaly calkowicie zakazone.Wyniki testu zebrane sa w tabeli 3.Nastepujace przyklady ilustruja sposób wytwa¬ rzania substancji czynnych srodka wedlug wyna¬ lazku.Przyklad II. Zwiazek o wzorze 12 15,9 g (0,1 mola) 2,6-dwumetylo-N-propargilo-ani- liny i 8 g (0,1 mola) pirydyny ogrzewa sie do wrze¬ nia w 100 ml czterowodorofuranu i ostroznie za¬ daje 13 g (0,1 mola) chlorku kwasu furano-2-karbo- ksylowego. Mieszanine miesza sie w ciagu 15 minut pod chlodnica zwrotna i zateza przez oddestylowy- wanie rozpuszczalnika w prózni. Pozostalosc roz¬ twarza sie w chlorku metylenu i przemywa woda.Faze organiczna oddziela sie, suszy nad siarczanem sodu i zateza. Pozostalosc krystalizuje po roztarciu z eterem naftowym. Otrzymuje sie 22,5 g (89°/o wy¬ dajnosci teoretycznej) 2,6-dwumetylo-N-(2-furoilo) - Tabela 3 Testowanie Phytophthora (pomidory) — dzialanie zapobiegawcze 10 15 20 Substancja czynna zwiazek o wzorze 15 (znany) zwiazek o wzorze 16 zwiazek o wzorze 17 zwiazek o wzorze 18 zwiazek o wzorze 19 zwiazek o wzorze 20 zwiazek o wzorze 21 zwiazek o wzorze 22 zwiazek o wzorze 23 zwiazek o wzorze 24 zwiazek o wzorze 25 zwiazek o wzorze 26 zwiazek o wzorze 27 Stopien porazenia w °/o przy stezeniu substan¬ cji czynnej 0,0005% 61 — — — — — — — — — — :-r- — 0,00025% 0 12 14 2 30 37 7 6 14 7. 10 29 Tabela 4 R* R« R» R4 R5 R° Temperatura topnienia °C CH3 CH3 CH3 CH3 C2H5 CH3 CH3 Cl CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH| CH8 CH8 CH8 C2H5 CH8 CH8 6—C2H5 6—CH3 6—CH3 6—CH3 6—C2H5 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—CH3 6—C2H5 6—CH3 6—CH3 H H H H H H H H H ' H H H H H H H H H H H H H H H H H H H H H H -H H H H H H H H H H CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH2 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 H H H H H H H H CH3 H H H H H H Br H H H H H H H H H H H H H H H H H H Br H H wzór 7 wzór 5 wzór 7 —CH2—O—CH8 —CH2—O—CH8 —CHC12 wzór 14 —CH2—O—CH3 wzór 6 —CH2O.CH3 —Cri20CH3 wzór 6 wzór 5 —COOCH3 wzór 7 wzór 7 —CH2OS02CH8 wzór 4 —CHClg —CH2SCH3 —CH2—SCN —C(CH3)=CH2 —CH2CH2OCH3 —CH=CH—CH3 —C3Ht—n —CH2OC8H7 —CaHT—i —COOCHa —CH2OC2H5 —cH2ocm3 —CH2OCH2C=CH —CH2SCH3 129—31 120—21 137—40 n2?: 1,5362 t.w.: 125°C/0,1 mm Hg 74 114—15 90—99 80 93—94 olej olej 84—86 129—30 63—65 235—37 (xHCL) 273—74 olej olej 81—82 n2*: 1,5470 69—70 «28. i23- 1 o- ,22.I23' ,22,5. 1,5272 1,5150 1,5377 1,5102 ng"": 1,5088 70—72 61—62 n2?: 1,5290 55—57 56—00 n*j: 1,5637124 785 17 18 -N-propargilo-aniliny o temperaturze topnienia 109— 112°C.Produkt wyjsciowy o wzorze 13 wytwarza sie w sposób nastepujacy: Wytwarzanie 2,6-dwumetylo-N-propargilo-aniliny prowadzi sie droga reakcji 2,6-dwumetylo-aniliny z bromkiem propargilu (opis patentowy St.Zjedn.Am. nr 4 001 325).W analogiczny sposób mozna wytwarzac zwiazki o wzorze 1 zebrane w tabeli 4.Zastrzezenia patentowe 1. Srodek grzybobójczy, znamienny tym, ze jako substancje czynna zawiera przynajmniej jedna pod¬ stawiona N-propargilo-aniline o ogólnym wzorze 1; w którym R1 oznacza atom wodoru, rodnik alkilowy lub atom chlorowca, R2 .oznacza atom wodoru lub rodnik alkilowy, R* oznacza atom wodoru lub rod¬ nik alkilowy, R4 oznacza atom wodoru lub rodnik alkilowy, R5 oznacza atom wodoru, rodnik alkilowy, atom chlorowca lub ewentualnie podstawiony rod¬ nik fenylowy, R6 oznacza rodnik czterowodorofury- lowy, tiofenylówy, czterowodorotiofenylowy, ewen¬ tualnie podstawiony grupa alkilowa rodnik izoksa¬ zolilowy, ewentualnie podstawiony przez grupe cy- janowa lub tiocyjanowa rodnik alkilowy, alkenylowy i alkinylowy, rodnik dwuchlorowcoalkilowy, oraz grupy —CH2—Az, —CH2—OR8, —CH2SR7, —OR7, —SR7, —CHz—OSOzR8, —COOR7 i grupe o wzorze 4,, przy czym R7 i R8 oznaczaja podstawiony chlorow¬ cem, grupa cyjanowa i tiocyjanowa rodnik alkilowy i ewentualnie podstawiony rodnikami alkilowymi 10 15 20 25 30 rodnik alkenylowy, alkinylowy i alkoksyalkilowy, R7 dodatkowo oznacza niepodstawiony rodnik alkilowy, a Az oznacza grupe pirazolilowa-1, 1,2,4-triazolilo- wa-1 i imidazolilowa-1. 2. Sposób wytwarzania podstawionych N-propar- gilo-anilin o wzorze 1, w którym R1 oznacza atom wodoru, rodnik alkilowy lub atom chlorowca, R2 oznacza atom wodoru lub rodnik alkilowy, R* ozna¬ cza atom wodoru lub rodnik alkilowy, R4 oznacza atom wodoru lub rodnik alkilowy, R5 oznacza atom wodoru, rodnik alkilowy, atom chlorwoca lub ewen¬ tualnie podstawiony rodnik fenylowy, R6 oiznacza rodnik czterowodoroiurylowy, tiofenylówy, cztero¬ wodorotiofenylowy, ewentualnie podstawiony grupa alkilowa rodnik izoksazolilowy, ewentualnie podsta¬ wiony przez grupe cyjanowa lulb tiocyjanowa rodnik alkilowy, alkenylowy i alkinylowy, rodnik dwuchlo¬ rowcoalkilowy, oraz grupy —CH2—Az, —CH2OR8, —CH2SR7, —OR7, —SR7, —CH2—OS02R8, —COOR7 i grupe o wzorze 4, przy czym R7 i R* oznaczaja podstawiony chlorowcem, grupa cyjanowa i tiocyja¬ nowa rodnik alkilowy, oraz ewentualnie podstawio¬ ny rodnikami alkilowymi rodnik alkenylowy, alki¬ nylowy i alkoksyalkilowy, R7 dodatkowo oznacza niepodstawiony rodnik alkilowy, a Az oznacza grupe pirazolilowa-1, 1,2,4-triazolilowa-l i imidazolilowa-1, znamienny tym, ze N-propargilo-aniliny o wzorze 2, w którym R1 .— R5 maja znaczenie wyzej podane, poddaje sie reakcji z chlorkami lufo bromkami wzgle¬ dnie bezwodnikami kwasowymi o wzorach 3a lub 3b, w których R6 ma znaczenie wyzej podane, w obecnosci rozcienczalnika i ewentualnie w obec¬ nosci srodka wiazacego kwas. pi I' * /H yZW—C =C—R5 ~N\ NC—R6 II 0 ¦WzOR 1 R4 R1 I / /CH-C^C-R5 WZ0R 2 -CH -°-o WZ0R 4 -CH-N N=N WZ0R 5 /N=| "CH~N\J WZ0R 6 WZ0R 8 WZ0R 9 WZ0R 10 R — C —CUBr) II 0 WZ0R 3a (R—C—UD II 2 0 WZ0R 3b /=N WZ0R ® WZ0R 11124 785 /CH3 o-< /CH,—C=CH CH3 || -O O WZÓR 12 CH3 / 3 XH,— C=CH CH3 U Ó-< \ CH, o-< \h3 "h WZÓR 13 CH, / \ N-0 WZÓR K 3 ,CH2—C —O —CH3 X —CH?—C II O WZÓR 15 CH, /CH3 :h — c = ch \ X—CH—N ^H3 II 2 VN O WZÓR 16 /CH3 —n; ch3 I /CH— C=CH \ CH, ^C—CH— N /, II 2 v // O WZÓR 17 .CH 3 /CH2— C=CH \ XC—CH-O—CH2-C=CH CH3 || O WZÓR 18 O PM 'I /N1 ,CH3 X — CH2—N | — N SCH, ^CH2—C=CH WZÓR 19 .CH — N 3 /CH2—C^CH NCH C— CH— SCH, Ln3 || 2 O WZÓR 20 CH, .CH, „Z"3 /CH— C=CH w }-\ \H3 J-CHCi2 O WZÓR 21 CH3 ru I y 3 /CH— C = CH \h3 c-ch-s-ch3 o WZÓR 22 CH, XH yn3 .CH —C = CH \ CH, X—CH?—N k O ^N^ J WZÓR 23 CH3 /CH, I / 3 .CH—C^CH S05H 1 3 S03H \ CH3 N(j-CH2-0-C2 ...2 . .,,3 L—O—CH,—CH,—O —CH, WZÓR 24124 785 CH, /CH3 /CH —C^CH ^CH—CH3 O WZÓR 25 CH3 ru I X ^ 7CH — C=CH —n; ACH3 XC-CH2-CH-CH3 O WZÓR 26 CH, CH, /CH — C = CH ^CH, CH, XC —CH WZÓR 27 /CH.— C =CH + Cl-CO-O + 2osadg - HCl SCHEMAT £H, <0-< CH3 || ^0^ 0 PLThe subject of the invention is a fungicide and a process for the preparation of new substituted N-propargyl anilines as active substances of the agent. It is known that haloacetanilides, for example the alkyl ester of N-chloroacetyl-N- (2,6-dimethylphenyl) -alanine or - glycine, can be successfully used to control plant mycoses (German description DOS 2,350,944 and US patent No. 3,780,090). Their action, however, especially at lower doses and concentrations, especially against the phytophthora species, is not always fully satisfactory. It has been found that the new substituted N-propargyl-anilines of the general formula I have strong fungicidal properties. is hydrogen, alkyl or halogen, Rf is hydrogen or alkyl, R * is hydrogen or alkyl, RA is hydrogen or alkyl, R6 is hydrogen, alkyl, halogen or optionally substituted a phenyl radical, R 'represents a tetrahydrofuryl, thiophenyl, tetrahydrophenyl radical, an optionally substituted isoxazolyl group with alkyl radicals, an optionally substituted cyano or thiocyanate radical, an alkyl, alkenyl and alkynyl radical, a dichaloalkyl group, as well as Az, -CH2- -OR8, -CHfSR *, -OR7, -SR7, -CH2-OSO2R8 -COOR7 and the group of formula IV, where R7 and R1 are halogen-substituted, a cyano group and a thiayano alkyl radical and an optionally alkyl-substituted alkenyl, alkynyl or alkoxyalkyl radical, R7 is furthermore an unsubstituted alkyl radical and Az is a pyrazolyl-1,2,4-triazolyl radical. 1 and imidazolyl-1. According to the invention, the new substituted N-propargyl anilines of formula I are obtained by N-propargylanilines of formula I in which R1 - R5 have the meaning given above, Reaction with chlorides or bromides or acid anhydrides of the formulas 3a or 3b, in which R6 is as defined above, in the presence of a diluent and optionally in the presence of an acid binding agent. The new substituted N-propargyl anilines exhibit strong fungicidal properties. and surprisingly, the new active substances are much more active than the known alkyl esters of N-chloroacetyl-N- (2.6 dimethylphenyl) -alanine or -glycine. The new substituted N-propargyl anilines are generally not defined in In this formula, R 1, R 1, R 1, R 4 and R 5 are preferably hydrogen and a straight or branched alkyl radical with 1 to 4 carbon atoms, R 1 is moreover preferably halogen, in particular fluorine, chlorine or bromine, R 5 it furthermore preferably represents a phenyl radical optionally substituted with a halogen, an alkyl radical of 1-4 carbon atoms and a nitro group, and represents a halogen atom, R6 is preferably a tetrahydrofuran group - 124 789u oooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo c «wcoc« c «eoc« coeocococoeoeo 05 05 Oi OS OJ 05 OJ 05 05 OJ Oi O * 05 OJ OS O) 05 05 OJ 05 O Cb 05 05 Oi O) 05 Oi OJ 05 Oi O) 05 O Oi Oi 05 05 05 OS Oi 05 OS Oi Oi OJ 05 05 05 Oi 05 05 Oi 05 Oi Oi 05 05 Oi Ci _. / -s 1 1 1 1 1 1 1 1 1 1 1 1 1 1 II 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 II 1 1 1 1 I 1 1 1 I ll 1 l 1 1 II 1 I 1 I 1 1 1 II 1 £ lcowcoeoc * coeoc * »c« eoe «cocoeocococ« cococ * eococococococococococoeococococo ffipHSffiKwHHHffiHWWWWHWHHWHwffiffiffi 1 co coceeocoeocococococoeocococo 1 co coceeocoeococococoeocococo * 1 Mococo 1 Mococo 1 Mococo 1 Mocococo 1 Mococo 1 Mococo 1 Mococo 1 Mococo 1 Mococo 1 Mococo 1 Mococo 1 Mococo 1 Mocococo 1 Mococo 1 * 1 Mococo 1 Mococo 3 1 1 1 1 ¦ M 3 * * 1 M 3 * number | | | | M ^^^ GM - ^^ I 1 1 1 1 M 3 * * 1 \ zzz \ g, oooooog, g, g, goog, g, g, oooooog, g, g, g, oog, g, g, oooooog , g, g. g, B og, g, g, oooooog, g. g, g, oo g. g, g, o owG ", PG ó <" owSBP0 oo ooog-oo ° Ko ow C can ^ because * & p f: ffi pgp yx f: K after? & p p pop j, pf ^ a 1 M £ P co .rr1 »eo?" 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LJ, - - - - _. - - -. - - - - - - - O) O) O) O) O) O) O) O) O) O) O) O ) O) O) O) Ml LM IIIIIIIIIII II I IIIII ITI [III [II III IIIII I III I IIIIIIIII II II ML opooooooooooopooooooooo < "ooooooooooooooooooooooooooooooooooooooooo XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX XXXXQX WKWWEWfflffiEWKfflEWWKEEti ^ KWE.ffiEEfflEEEffl WG 09» ffiffiffiooooooooooooo is 00 Ul • SIS "because a- t »o im i <.G & ft ffi ffi ffi -» - »fu hj O this o X 8 oo Ml HM o g. oooo g. a ^ oawwi W -O Oo ¦ £,« OQ "wo O w 3 1 1 1 1 1 g, ooooo «XXOXX en to / - * \ to ( o O ° n SO w Q co "Q * ° ff ^ tr X * * z NO _ _» -l »-s» -i «-i H (O 00 ^ n KM t» to OO 1111113 3 3 3 oooooog , g, g, gO OXUO in XM CO 00 ^ 3 3 3 6 g, * fc? to _ OO ^ X * to I 8 to IIIIIIOOOOOOKXOXXX oog Q every% 5 wGM after 3 3 NNM CO 00 ^ 'o X 1 o I o X l I 3 5: o & g- b ^ • O124 785 7 8 1 1 CH8 CH3 CH8 CH3 CH8 CH8 CH3 CH8 CH8 CH3 CH8 CH3 CH8 • CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 ^ H8 CH8 CH8 CH8 CH8 CHg CH8 CH3 CH3 CH3 CH8, CH3 CH8 CH8 CH8 | CH8 CH8 CH8 CH8 CH8 CH8 CH8 C2H5 1 CeH5 C2H5 c ^ CsHg C * H5 CaU C2H5 C * H5 C * H5 C2H5 C8H5 C2H5 C2H5 C * H5 "C * H5 C2H5 | C2H5 1 1 2 l 6 — C2H5 6 — C2H5 6 —C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 I 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6— C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C * H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 I 6 — C2H5 6 —C2H5 6 — C2H5 | 6-CH, 6 — C2H5 6 — C2H5 6 — CfHs 6 — C2H5 C — C2H5 1 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H11 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 | 3 THHHHHHHHHHHHH * HHH 1 * HHHHHHHHHHHHHHHHHH hhhhhhhhhhh HHHHHHHHHHHHHHHHHHHH 1 1 4 1 HHH HHHH 1 HHHHHHHHHH CH8 CH3 CH3 CH3 CH3 CH3 CH3 CH8 CH8 .CHg H HHHHHHHHHHHHHHHHHHHHH HHHHHHHH CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH3 | 1 5 1 CH3 CH3 CH8 CH8 CH3 CH3 CH3 Br Br Br Br »Br Br Br Br Br Br Br Br Br Br Br Br Br Br Br Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl J J J J J J J J J J H H H H H H H H H H H H H H H H H H H | 1 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCH3 formula 8 —CH2SCH3 formula 4 —CH2OCH3 formula 5 formula 6 —CH2OC2H5 1 —CH2OS02CH3 1 —CHCI2 '—COOCHg formula 8 —CH2SCHg formula 4 —CH2OCH3 formula 5 formula 6 —CH2OC2CH5 CHCI2 —COOCH3 formula 8 —CH2SCH2J formula 4 CH2OCH3 | formula 5 formula 6 —CH2OC2H5 —CH2OS02CH3 —CHCI2 —COOCH3 formula 8 —CH2SCH3 formula 4 —CH2OCH3 formula 5 formula 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCH3 formula 8 —CH2SCH3 J formula 4 1 —CH2OCH3 formula 5 formula 6 —CH2OC2H5 —CHC12 —COOCHg 1 formula 8 —CH2SCH3 formula 4 —CH2 — OCH3 formula 5 formula 6 —CH20C2H5 —CH2OS02CH3 —CHC12 —COOCH8 formula 8 '124 785 10 1 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C, H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 CZH5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6— * C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 —C2H5 6 — C2H5 6 — C2H5 6 —- C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 ^ C2Hs 6 — C2H5 6 — C2H5 6 — C2H5 6— C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6-C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 — C2H5 6 6-C2H5 C2H5 6-C2H5 3 HHHHHHHHHHHHHHHHHHHHH HHHHHHHHHHHHHHHHHHHHH HHHHHHHHHH 4 CH3 CH8 HHHHHHHHHHHH hhhhhh HH CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 5 HHHHHHHHHHHHHHHHHHHH HH CH3 CH3 CH3 CH3 CH3 CH3 CH8 CH3 CH3 CH3 Br Br Br Br Br Br Br Br • Br Br Br Br Br Br Br Br Br Br Cl x Cl Cl Cl Cl Cl Cl Cl JJJJJJJJJJ 6 —CH2SCH3 formula 4 —CH2OCH3 formula 5 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCH3 formula 8 —CH2SCH3 formula 4 - CH2OCH8 formula 5 formula 6 —CH2OC2H5 —CHzOSOaCH * —CHC12 —COOCHg formula 8 —CH2SCH3 formula 4 —CH2OCH8 1 formula 5 formula 6 —CH2OC2H5 —CHaPSOaCHs —CHC12 —COOCHg formula 8 —CH2SCH3 formula 4 —CH2OCH3 formula 5 visor 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCH3 formula 8 —CH2SCH3 formula 4 —CH2OCHa formula 5 formula 6 —CH2OC2H5 —CH2OS02CH3 —CHC12 —COOCHg formula 8 —CH2SCH3 thiophenyl, tetrahydrophenyl, optionally methyl or ethyl substituted isoxazolyl and optionally substituted cyano or thiocyanin alkyl radical with 1-4 carbon atoms and alkenyl and alkynyl radicals each having 2 to 4 carbon atoms, more preferably denotes a dichaloalkyl group with 1-2 carbon atoms, the halogen atoms being preferably fluorine and chlorine, and also denotes the groups -CH2-Az, -CHr66 -OR8, -CH2-SR7, -OR7, -SR7, -CH2-OSO2R8, -COOR7 and the group of formula VII, Az is preferably 1, 1,2,4-triazolyl-1-pyrazolyl and 1-imidazolyl-1, R7 is preferably optionally substituted with halogen, especially fluorine, chlorine. and rhodium, cyano and thiocyanin alkyl radicals having 1-4 carbon atoms Ia and an alkoxyalkyl group with 1-4 carbon atoms in each alkyl radical. Particularly preferred are the substituted N-propar-124 785 11 12 glycylanilines of the formula I, in which R1, R2 and R3 are hydrogen. , methyl, ethyl, isopropyl radicals, 2nd order. butyl and IH-rows. butyl groups, Ri is further chlorine or bromine, R4 is a hydrogen atom, a methyl or ethyl radical, R5 is a hydrogen atom, a methyl, ethyl, phenyl, bromine, chlorine or iodine radical, and R6 is a 2-thienyl, 2-tetrahydrofuryl group , 5-methylisoxazolyl-3, methoxymethyl, ethoxymethyl, allyloxymethyl, propargiLoxymethyl, ethoxymethoxymethyl, methylthiomethyl, methoxy, ethoxy, methylthio, methylsulfonyloxymethyl, methoxycarbonyl, methoxycarbonyl, dimethyl carbonyl , imidazolyl-1-methyl, 1,2,4-triazolyl-1-methyl and tetrahydro-pyran--2-yloxy-methyl. The compounds of formula I listed in Table 1 are particularly preferred. , 6-dimethyl-N-propargyl aniline and furan-2-carboxylic acid chloride as starting compounds, the course of the reaction is shown in the diagram in the figure. N-propargylanilines used as starting compounds are generally defined by the formula 2. pattern Wherein R1, R2, R *, R4 and R5 are preferably the groups already mentioned as being preferred in discussing the compounds of formula 1. N-propargyl anilines of formula II are known in part (US Pat. Nos. 3,535,377 and 4,001,325), or they can be prepared in a known manner, e.g. by reacting the corresponding anilines with halides of the formula V or with the corresponding propargyl sulfonates, for example mesylates or tosylates, in the presence of which bind an acid, for example sodium or potassium carbonate, optionally in the presence of an inert organic solvent such as ethanol at a temperature of 20-150 ° C, preferably an excess of aniline may be used. , in which R4 is a methyl radical, can also be obtained by reacting the corresponding aniline with acetylene in the presence of copper acetylenepium under pressure (Liebigs Ann. Chem. 596, 1 (1955)). Examples of compounds of formula 2 are compounds collected in Table 2. The chlorides or bromides or acid anhydrides used as starting compounds are generally defined by the formulas 3a and 3b. In these formulas, R6 preferably denotes the groups already mentioned as being preferred in discussing the compounds of formula 1. Chlorides or acid bromides or anhydrides of the formulas 3a and 3b are compounds generally known in organic chemistry. Inert solvents are preferably used as diluents. organic. These include, preferably, ketones such as diethyl ketone, in particular acetone and methyl ethyl ketone, nitriles such as propionitrile, in particular acetonitrile, ethers such as tetrahydrofuran or dioxane, aliphatic and aromatic hydrocarbons such as petroleum ether, benzene. , toluene or xylene, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene, and esters such as ethyl acetate. The reactions may optionally be carried out in the present Table 2 and R1 CHg C2H5 C2H5 C (CH3) 3 CHa CU, Cl Cl CH * CH3 C2H5 C2H5 CH3 C2H5 C2H5 CH * C2H5 C2H5 CHa C2H5 1 C2H5 1 CHo C2H5 C2H5 | R2 6 — CH3 6 — C2H5 6 — CH3 H 3 — CH3 5 — CHa 1 6 — CH3 6 — C (CH3) 3 3 — CH3 6 — CH3 6 — C2H5 6 — CH3 6 — CH3 6 — C2H5 6 — CH3 6 —CH3 6 — C2H5 6 — CH3 6-CHg, 6 — C2H5 6 — CH3 6-CH3 6 — C2H5 6 — CH3 R »HHHHHHHB 6 - <: h3 HHHHHHHHHHHHHHH | | R4 H H H H H H H H H CHs CHs CHs C2H5 C2H5 C2Es H H H H H H CHa CH3 CH3 1 R5 H I.H H H H: h H H H H H H H H H 'H CH3 CH3 CH3 formula 11 formula 11 formula 11 CH3 CH3 CH3 carry acid binders (hydrogen chloride acceptors). Any known acid binders can be used here. These preferably include organic bases such as tertiary amines, for example triethylamine or pyridine, and furthermore inorganic bases such as alkali metal hydroxides and alkali metal carbonates. A catalyst such as dimethylformamide may also be used. The reaction temperature may vary over a wide range. In general, the reactions are carried out at temperatures between 0 and 120 ° C., preferably between 20 and 100 ° C.. The reactants are preferably introduced in molar amounts. The compounds of formula (1) are distinguished in a known manner. The end products are distinguished in a known manner. The new active substances have strong microbicidal properties and can be used in practice to combat undesirable microorganisms. These substances are suitable for use as plant protection agents. Plant protection fungicides are used to control Plasmodiophoaromycetes, Oomycetes, Chytridiomycetes, Zygpmycetes, Ascomycetes, Basidiomycetes, Deuteromycetes. Due to the fact that the plants exhibit a good volume ratio. to the new active substances in the concentrations necessary for the control of plant diseases, these substances can be used for the treatment of the above-ground parts of plants, seedlings and seeds as well as the soil. The new active substances as plant protection agents can be used with good results in the control of Oomycetes , eg against pathogens of potato blight on tomatoes and potatoes (Phytophthora infestans). It should be emphasized in particular that the new active substances have not only a preventive effect, but also a healing / repelling effect. Moreover, they have systemic properties. Such plants can therefore be protected against fungal contamination if the active substances travel through the soil and the roots or through the seed to the above-ground parts of the plants. The active substances can be converted into known preparations such as solutions, emulsions, wettable powders. , suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed powders, natural and synthetic substances impregnated with the active substance, fine capsules in polymeric substances and seed coatings, furthermore preparations with a combustible liner, such as cartridges, charges, and spirals for smoke and others, and ULV preparations for nebulizing cold and heat spraying. These preparations can be prepared in a known manner, for example by mixing of the active ingredient with diluents, i.e. liquid solvents under pressure, with liquefied gases and / or solid carriers, or with surfactants, for example emulsifiers and / or dispersants and / or foaming agents. In the case of the use of water as an extender, organic solvents can, for example, be used as dissolving aids. Liquid solvents are generally aromatic compounds such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons such as chlorine. - robenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. Liquefied gaseous diluents and carriers are liquids which are gases at normal temperature and pressure, such as aerosol propellants such as halogenated-. dory, as well as butane, propane, nitrogen and carbon dioxide. Natural rock powders such as kaolins, clays, talcum, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic mineral powders such as acid are used as permanent carriers. finely divided silica, alumina and silicates: Crushed and fractionated natural powders such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flour as well as synthetic granules of inorganic and organic flour are used as solid carriers for the granules. granules of organic material such as sawdust, coconut lupines, corn cobs, and tobacco sticks. Nonionic and anionic emulsifiers and / or foaming agents, such as polyoxyethylene fatty acid esters, are used as emulsifiers and / or foaming agents. polyoxyethylene and fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. As dispersants, for example, lignin sulfite lugs and methyl cellulose are used. The preparations may contain adhesion promoters such as carboxymethyl cellulose, natural and synthetic polymers, powdered, granular or latex, such as gum arabic, alcohol. polyvinyl and polyvinyl acetate. • Dyes such as inorganic pigments, for example, iron oxide, titanium oxide, iron blue, and organic dyes, such as alizarin, azo and metallophthalyanine dyes, as well as substances can be added. Trace salts such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts. The preparations generally contain 0.1-95% by weight of active ingredient, preferably 0.5-90% by weight. 20 New active ingredients may be present. in preparations or in various application forms, mixed with other known active substances, such as fungicides, bactericides, insecticides, acaricides, nematodes, etc. Anticides, anti-nulling substances, growth substances, plant nutrients and soil improvers. The active substances can be used alone, in the form of concentrates or prepared from them by further diluting application forms such as ready-to-use. for use solutions, emulsions, suspensions, powders, pastes and granules. The agents are used in the usual manner, for example by watering, dipping, spraying, spraying, nebulizing, steaming, injecting, sludging, coating, dusting, scattering, dry dressing, wet dressing, wet dressing, slurry dressing or encrustation. During the treatment of plant parts, the concentration of the active compound in the application forms can vary widely. In general, these concentrations are in the range from 1 to 0.0001% by weight, preferably from 0.5 to 0% by weight. For the treatment of the seed, the amount of active ingredient used is generally from 0.001 to 50 g per kg of seeds, preferably 0. 01-10 g. For the treatment of the soil, the active substances are used in a concentration of 0.00001-0.1% by weight, preferably 0.0001-0.02%. The following examples illustrate the invention. I. Testing of Phytophthora (tomatoes) - preventive action. Solvent: 4.7 parts by weight of acetone. Emulsifier: 0.3 parts by weight of polyglycol alkylaryl ether. 1 part by weight of the substance is mixed to obtain a favorable formulation of the active substance. with the specified amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. The spraying liquid is sprayed; until the drainage of young tomato plants. After the tomato plants have been sprayed dry, the aqueous spore suspension of Phytophthora infestans is forbidden and kept in a humid chamber with 100% elevated air humidity and a temperature of about 20 ° C. After 15 124 785 16 or 3 days it is determined degree of attack of tomato plants. The estimated values obtained are converted into percentages, with 0% indicating no attack and 100% indicating that the plants are completely contaminated. The results of the test are summarized in Table 3. The following examples illustrate the preparation of the active ingredients of the preparation. according to the invention. Example II. The compound of formula 12 15.9 g (0.1 mol) of 2,6-dimethyl-N-propargylaniline and 8 g (0.1 mol) of pyridine is heated to boiling in 100 ml of tetrahydrofuran and carefully ¬ gives 13 g (0.1 mol) of furan-2-carboxylic acid chloride. The mixture was stirred for 15 minutes under reflux, and concentrated by distillation of the solvent under vacuum. The residue is taken up in methylene chloride and washed with water. The organic phase is separated, dried over sodium sulfate and concentrated. The residue crystallizes on trituration with petroleum ether. There are obtained 22.5 g (89% of theoretical yield) of 2,6-dimethyl-N- (2-furoyl). Table 3. Testing of Phytophthora (tomatoes) - preventive action 10 15 20 Active substance of the compound of formula 15 ( known) a compound of formula 16 a compound of formula 17 a compound of formula 18 a compound of formula 19 a compound of formula 20 a compound of formula 20 a compound of formula 22 a compound of formula 23 a compound of formula 24 a compound of a formula 25 a compound of a formula 27 Degree of fire in% at the concentration of the active substance 0.0005% 61 - - - - - - - - - -: -r- - 0.00025% 0 12 14 2 30 37 7 6 14 7. 10 29 Table 4 R * R "R" R4 R5 R ° Melting point ° C CH3 CH3 CH3 CH3 C2H5 CH3 CH3 Cl CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH8 CH | CH8 CH8 CH8 C2H5 CH8 CH8 6 — C2H5 6 — CH3 6 — CH3 6 — CH3 6 — C2H5 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6— CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — CH3 6 — C2H5 6 — CH3 6 —CH3 HHHHHHHH 'HHHHHHHHHHHHHHHHHHHHHH H -HHHHHHHHHH CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH2 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 HHHHHHH CHH — HHHHH — HHHHH — Br HHHH — Br HHHH — HHHH — HHHH — CH8 —CHC12 formula 14 —CH2 — O — CH3 formula 6 —CH2O.CH3 —Cri20CH3 formula 6 formula 5 —COOCH3 formula 7 formula 7 —CH2OS02CH8 formula 4 —CHClg —CH2SCH3 —CH2 — SCN —C (CH3) = CH2 —CH2CH2OCH3 —CH = CH — CH3 —C3Ht — n —CH2OC8H7 —CaHT — and —COOCHa —CH2OC2H5 —cH2ocm3 —CH2OCH2C = CH —CH2SCH3 129—31 120—21 137—40 n2 ?: 1.5362 t: 125 ° C / 0 0.1 mm Hg 74 114-15 90-99 80 93-94 oil oil 84-86 129-30 63-65 235-37 (xHCL) 273-74 oil oil 81-82 n2 *: 1.5470 69-70 " 28. i23- 1 o-, 22.I23 ', 22.5. 1.5272 1.5150 1.5377 1.5102 ng "": 1.5088 70—72 61—62 n2 ?: 1.5290 55—57 56—00 n * j: 1.5637124 785 17 18 -N- propargyl-aniline, mp 109-112 ° C. The starting product of formula 13 is prepared as follows: The preparation of 2,6-dimethyl-N-propargyl-aniline is carried out by reacting 2,6-dimethyl aniline with propargyl bromide ( U.S. Patent No. 4,001,325). The compounds of the formula 1 listed in Table 4 can be prepared in an analogous manner. Claims 1. A fungicide, characterized in that at least one substituted N- propargylaniline of general formula I; where R1 is a hydrogen atom, an alkyl radical or a halogen atom, R2 is a hydrogen atom or an alkyl radical, R * is a hydrogen atom or an alkyl radical, R4 is a hydrogen atom or an alkyl radical, R5 is a hydrogen atom, an alkyl radical, halogen or an optionally substituted phenyl radical, R 6 is tetrahydrofuryl, thiophenyl, tetrahydrogen thiophenyl, an optionally substituted alkyl group, an isoxazolyl radical, optionally substituted with a cyano or thiocyano group, an alkyl, alkenyl, alkynyl and alkynyl radical and the groups —CH2 — Az, —CH2 — OR8, —CH2SR7, —OR7, —SR7, —CHz — OSOzR8, —COOR7 and the group of formula 4, where R7 and R8 are halogen-substituted, cyano and thiocyano an alkyl radical and an optionally substituted alkenyl, alkynyl and alkoxyalkyl radical, R7 additionally is an unsubstituted alkyl radical and Az is pyrazolyl-1, 1,2,4-triazolyl-1 and imidazolyl-1. 2. The method for the preparation of substituted N-propargyl-anilines of formula I, wherein R1 is a hydrogen atom, an alkyl radical or a halogen atom, R2 is a hydrogen atom or an alkyl radical, R * is a hydrogen atom or an alkyl radical, and R4 is a hydrogen atom or an alkyl radical, R5 is a hydrogen atom, an alkyl radical, a halogen atom or an optionally substituted phenyl radical, R6 is a tetrahydrouryl, thiophenyl, tetrahydrophenyl, or an optionally substituted alkyl group, an isoxazolyl radical, optionally substituted with a 10 cyanide group. a thiocyano alkyl, alkenyl and alkynyl radical, a dichloroalkyl radical, and groups —CH2 — Az, —CH2OR8, —CH2SR7, —OR7, —SR7, —CH2 — OSO2R8, —COOR7 and the group of formula 4, where R7 and R * denote a halogen-substituted cyano and thiocyanin alkyl radical, and an optionally substituted alkenyl, alkynyl and alkoxyalkyl radical, and R7 additionally represents an unsubstituted alkyl radical and Az is pyrazolyl-1, 1,2,4-triazolyl-1 and imidazolyl-1, characterized in that the N-propargyl-anilines of formula 2, wherein R 1 - R 5 are as defined above, are reacted with chlorides or bromides or acid anhydrides of the formulas 3a or 3b, in which R6 is as defined above, in the presence of a diluent and possibly in the presence of an acid binding agent. pi I '* / H yZW — C = C — R5 ~ N \ NC — R6 II 0 ¦Formula 1 R4 R1 I / / CH-C ^ C-R5 WZ0R 2 -CH - ° -o WZ0R 4 -CH-N N = N WZ0R 5 / N = | "CH ~ N \ J WZ0R 6 WZ0R 8 WZ0R 9 WZ0R 10 R - C —CUBr) II 0 WZ0R 3a (R — C — UD II 2 0 WZ0R 3b / = N WZ0R ® WZ0R 11124 785 / CH3 o- </ CH , —C = CH CH3 || -OO FORMULA 12 CH3 / 3 XH, - C = CH CH3 U Ó- <\ CH, o- <\ h3 "h FORMULA 13 CH, / \ N-0 FORMULA K 3, CH2 —C —O —CH3 X —CH? —C II O FORMULA 15 CH, / CH3: h - c = ch \ X — CH — N ^ H3 II 2 VN O FORMULA 16 / CH3 —n; ch3 I / CH— C = CH \ CH, ^ C — CH— N /, II 2 v // O FORMULA 17. CH 3 / CH2— C = CH \ XC — CH-O — CH2-C = CH CH3 || O FORMULA 18 O PM 'I / N1, CH3 X - CH2 — N | - N SCH, ^ CH2 — C = CH MODEL 19 .CH - N 3 / CH2 — C ^ CH NCH C— CH— SCH, Ln3 || 2 O MODEL 20 CH, .CH, "Z" 3 / CH— C = CH w} - \ \ H3 J-CHCi2 O FORMULA 21 CH3 ru I y 3 / CH— C = CH \ h3 c-ch-s-ch3 o FORMULA 22 CH, XH yn3. CH — C = CH \ CH, X — CH? —N k O ^ N ^ J FORMULA 23 CH3 / CH, I / 3. CH — C ^ CH SO 5H 1 3 SO 3 H \ CH3 N (j- CH2-0-C2 ... 2. ,, 3 L — O — CH, —CH, —O — CH, FORMULA 24124 785 CH, / CH3 / CH —C ^ CH ^ CH — CH3 FOR FORMULA 25 CH3 ru IX ^ 7CH - C = CH — n; ACH3 XC-CH2-CH-CH3 O FORMULA 26 CH, CH, / CH - C = CH ^ CH, CH, XC —CH FORMULA 27 / CH. C = CH + Cl -CO-O + 2sadg - HCl SCHEME H, <0- <CH3 || ^ 0 ^ 0 PL

Claims (2)

Zastrzezenia patentowe 1. Srodek grzybobójczy, znamienny tym, ze jako substancje czynna zawiera przynajmniej jedna pod¬ stawiona N-propargilo-aniline o ogólnym wzorze 1; w którym R1 oznacza atom wodoru, rodnik alkilowy lub atom chlorowca, R2 .oznacza atom wodoru lub rodnik alkilowy, R* oznacza atom wodoru lub rod¬ nik alkilowy, R4 oznacza atom wodoru lub rodnik alkilowy, R5 oznacza atom wodoru, rodnik alkilowy, atom chlorowca lub ewentualnie podstawiony rod¬ nik fenylowy, R6 oznacza rodnik czterowodorofury- lowy, tiofenylówy, czterowodorotiofenylowy, ewen¬ tualnie podstawiony grupa alkilowa rodnik izoksa¬ zolilowy, ewentualnie podstawiony przez grupe cy- janowa lub tiocyjanowa rodnik alkilowy, alkenylowy i alkinylowy, rodnik dwuchlorowcoalkilowy, oraz grupy —CH2—Az, —CH2—OR8, —CH2SR7, —OR7, —SR7, —CHz—OSOzR8, —COOR7 i grupe o wzorze 4,, przy czym R7 i R8 oznaczaja podstawiony chlorow¬ cem, grupa cyjanowa i tiocyjanowa rodnik alkilowy i ewentualnie podstawiony rodnikami alkilowymi 10 15 20 25 30 rodnik alkenylowy, alkinylowy i alkoksyalkilowy, R7 dodatkowo oznacza niepodstawiony rodnik alkilowy, a Az oznacza grupe pirazolilowa-1, 1,2,4-triazolilo- wa-1 i imidazolilowa-1. 2. Sposób wytwarzania podstawionych N-propar- gilo-anilin o wzorze 1, w którym R1 oznacza atom wodoru, rodnik alkilowy lub atom chlorowca, R2 oznacza atom wodoru lub rodnik alkilowy, R* ozna¬ cza atom wodoru lub rodnik alkilowy, R4 oznacza atom wodoru lub rodnik alkilowy, R5 oznacza atom wodoru, rodnik alkilowy, atom chlorwoca lub ewen¬ tualnie podstawiony rodnik fenylowy, R6 oiznacza rodnik czterowodoroiurylowy, tiofenylówy, cztero¬ wodorotiofenylowy, ewentualnie podstawiony grupa alkilowa rodnik izoksazolilowy, ewentualnie podsta¬ wiony przez grupe cyjanowa lulb tiocyjanowa rodnik alkilowy, alkenylowy i alkinylowy, rodnik dwuchlo¬ rowcoalkilowy, oraz grupy —CH2—Az, —CH2OR8, —CH2SR7, —OR7, —SR7, —CH2—OS02R8, —COOR7 i grupe o wzorze 4, przy czym R7 i R* oznaczaja podstawiony chlorowcem, grupa cyjanowa i tiocyja¬ nowa rodnik alkilowy, oraz ewentualnie podstawio¬ ny rodnikami alkilowymi rodnik alkenylowy, alki¬ nylowy i alkoksyalkilowy, R7 dodatkowo oznacza niepodstawiony rodnik alkilowy, a Az oznacza grupe pirazolilowa-1, 1,2,4-triazolilowa-l i imidazolilowa-1, znamienny tym, ze N-propargilo-aniliny o wzorze 2, w którym R1 .— R5 maja znaczenie wyzej podane, poddaje sie reakcji z chlorkami lufo bromkami wzgle¬ dnie bezwodnikami kwasowymi o wzorach 3a lub 3b, w których R6 ma znaczenie wyzej podane, w obecnosci rozcienczalnika i ewentualnie w obec¬ nosci srodka wiazacego kwas. pi I' * /H yZW—C =C—R5 ~N\ NC—R6 II 0 ¦WzOR 1 R4 R1 I / /CH-C^C-R5 WZ0R 2 -CH -°-o WZ0R 4 -CH-N N=N WZ0R 5 /N=| "CH~N\J WZ0R 6 WZ0R 8 WZ0R 9 WZ0R 10 R — C —CUBr) II 0 WZ0R 3a (R—C—UD II 2 0 WZ0R 3b /=N WZ0R ® WZ0R 11124 785 /CH3 o-< /CH,—C=CH CH3 || -O O WZÓR 12 CH3 / 3 XH,— C=CH CH3 U Ó-< \ CH, o-< \h3 "h WZÓR 13 CH, / \ N-0 WZÓR K 3 ,CH2—C —O —CH3 X —CH?—C II O WZÓR 15 CH, /CH3 :h — c = ch \ X—CH—N ^H3 II 2 VN O WZÓR 16 /CH3 —n; ch3 I /CH— C=CH \ CH, ^C—CH— N /, II 2 v // O WZÓR 17 .CH 3 /CH2— C=CH \ XC—CH-O—CH2-C=CH CH3 || O WZÓR 18 O PM 'I /N1 ,CH3 X — CH2—N | — N SCH, ^CH2—C=CH WZÓR 19 .CH — N 3 /CH2—C^CH NCH C— CH— SCH, Ln3 || 2 O WZÓR 20 CH, .CH, „Z"3 /CH— C=CH w }-\ \H3 J-CHCi2 O WZÓR 21 CH3 ru I y 3 /CH— C = CH \h3 c-ch-s-ch3 o WZÓR 22 CH, XH yn3 .CH —C = CH \ CH, X—CH?—N k O ^N^ J WZÓR 23 CH3 /CH, I / 3 .CH—C^CH S05H 1 3 S03H \ CH3 N(j-CH2-0-C2 ...Claims 1. A fungicide, characterized in that the active ingredient is at least one substituted N-propargylaniline of the general formula I; where R1 is a hydrogen atom, an alkyl radical or a halogen atom, R2 is a hydrogen atom or an alkyl radical, R * is a hydrogen atom or an alkyl radical, R4 is a hydrogen atom or an alkyl radical, R5 is a hydrogen atom, an alkyl radical, halogen or an optionally substituted phenyl radical, R 6 is tetrahydrofuryl, thiophenyl, tetrahydrogen thiophenyl, an optionally substituted alkyl group, an isoxazolyl radical, optionally substituted with a cyano or thiocyano group, an alkyl, alkenyl, alkynyl and alkynyl radical and the groups —CH2 — Az, —CH2 — OR8, —CH2SR7, —OR7, —SR7, —CHz — OSOzR8, —COOR7 and the group of formula 4, where R7 and R8 are halogen-substituted, cyano and thiocyano an alkyl radical and an optionally substituted alkenyl, alkynyl and alkoxyalkyl radical, R7 additionally is an unsubstituted alkyl radical and Az is pyrazolyl-1, 1,2,4-triazolyl-1 and imidazolyl-1. 2. The method for the preparation of substituted N-propargyl-anilines of formula I, wherein R1 is a hydrogen atom, an alkyl radical or a halogen atom, R2 is a hydrogen atom or an alkyl radical, R * is a hydrogen atom or an alkyl radical, and R4 is a hydrogen atom or an alkyl radical, R5 is a hydrogen atom, an alkyl radical, a halogen atom or an optionally substituted phenyl radical, R6 is a tetrahydrouryl, thiophenyl, tetrahydrophenyl, or an optionally substituted alkyl group, an isoxazolyl radical, optionally substituted with a 10 cyanide group. a thiocyano alkyl, alkenyl and alkynyl radical, a dichloroalkyl radical, and groups —CH2 — Az, —CH2OR8, —CH2SR7, —OR7, —SR7, —CH2 — OSO2R8, —COOR7 and the group of formula 4, where R7 and R * denote a halogen-substituted cyano and thiocyanin alkyl radical, and an optionally substituted alkenyl, alkynyl and alkoxyalkyl radical, and R7 additionally represents an unsubstituted alkyl radical and Az is pyrazolyl-1, 1,2,4-triazolyl-1 and imidazolyl-1, characterized in that the N-propargyl-anilines of formula 2, wherein R 1 - R 5 are as defined above, are reacted with chlorides or bromides or acid anhydrides of the formulas 3a or 3b, in which R6 is as defined above, in the presence of a diluent and possibly in the presence of an acid binding agent. pi I '* / H yZW — C = C — R5 ~ N \ NC — R6 II 0 ¦Formula 1 R4 R1 I / / CH-C ^ C-R5 WZ0R 2 -CH - ° -o WZ0R 4 -CH-N N = N WZ0R 5 / N = | "CH ~ N \ J WZ0R 6 WZ0R 8 WZ0R 9 WZ0R 10 R - C —CUBr) II 0 WZ0R 3a (R — C — UD II 2 0 WZ0R 3b / = N WZ0R ® WZ0R 11124 785 / CH3 o- </ CH , —C = CH CH3 || -OO FORMULA 12 CH3 / 3 XH, - C = CH CH3 U Ó- <\ CH, o- <\ h3 "h FORMULA 13 CH, / \ N-0 FORMULA K 3, CH2 —C —O —CH3 X —CH? —C II O FORMULA 15 CH, / CH3: h - c = ch \ X — CH — N ^ H3 II 2 VN O FORMULA 16 / CH3 —n; ch3 I / CH— C = CH \ CH, ^ C — CH— N /, II 2 v // O FORMULA 17. CH 3 / CH2— C = CH \ XC — CH-O — CH2-C = CH CH3 || O FORMULA 18 O PM 'I / N1, CH3 X - CH2 — N | - N SCH, ^ CH2 — C = CH MODEL 19 .CH - N 3 / CH2 — C ^ CH NCH C— CH— SCH, Ln3 || 2 O MODEL 20 CH, .CH, "Z" 3 / CH— C = CH w} - \ \ H3 J-CHCi2 O FORMULA 21 CH3 ru I y 3 / CH— C = CH \ h3 c-ch-s-ch3 o FORMULA 22 CH, XH yn3. CH — C = CH \ CH, X — CH? —N k O ^ N ^ J FORMULA 23 CH3 / CH, I / 3. CH — C ^ CH SO 5H 1 3 SO 3 H \ CH3 N (j- CH2-0-C2 ... 2 . .,,3 L—O—CH,—CH,—O —CH, WZÓR 24124 785 CH, /CH3 /CH —C^CH ^CH—CH3 O WZÓR 25 CH3 ru I X ^ 7CH — C=CH —n; ACH3 XC-CH2-CH-CH3 O WZÓR 26 CH, CH, /CH — C = CH ^CH, CH, XC —CH WZÓR 27 /CH.— C =CH + Cl-CO-O + 2osadg - HCl SCHEMAT £H, <0-< CH3 || ^0^ 0 PL2. . ,, 3 L — O — CH, —CH, —O — CH, FORMULA 24124 785 CH, / CH3 / CH —C ^ CH ^ CH — CH3 FOR FORMULA 25 CH3 ru AND X ^ 7CH - C = CH — n; ACH3 XC-CH2-CH-CH3 O FORMULA 26 CH, CH, / CH - C = CH ^ CH, CH, XC —CH FORMULA 27 / CH. C = CH + Cl-CO-O + 2sadg - HCl SCHEME £ H, <0- <CH3 || ^ 0 ^ 0 PL
PL1979219330A 1978-10-31 1979-10-30 Fungicide and method of manufacture of substituted n-propargylanilines PL124785B1 (en)

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DE19782847287 DE2847287A1 (en) 1978-10-31 1978-10-31 SUBSTITUTED N-PROPARGYL ANILINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES
DE19792927461 DE2927461A1 (en) 1979-07-06 1979-07-06 N-Acyl-n-propargyl-aniline derivs. - useful as agricultural fungicides

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EP0028465A1 (en) * 1979-11-02 1981-05-13 Imperial Chemical Industries Plc Acylanilide compounds, methods for their preparation, compositions containing them, and processes for combatting fungi
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